Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/08—Heat treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

• This invention relates to a method for the manufacture of articles of substantially unstretched polypivalolactone having improved physical properties and to the improved articles thus obtained.
• British Pat. No. 1,055,740 discloses the preparation of articles such as threads, fibers, tapes, and films comprising polypivalolactone.
• articles such as threads, fibers, tapes, and films comprising polypivalolactone.
• fibers, tapes, and films will be cold stretched, thereby imparting a higher degree of orientation to the polymer molecules, so as to improve the tensile properties. While such cold stretching does improve the tensile properties, there is still a need to improve these properties even further. Also, there are occasions when it is expensive or difficult to cold stretch the formed article for a multitude of reasons.
• the present invention is directed to a method for improving the tensile properties of articles of polypivalolactone wherein the cold stretching techniques are obviated, i.e., the polypivalolactone articles are substantially in the unstretched condition.
• Such articles may be obtained from polypivalolactone sheets, rods, nibs, granules, powder, flakes and the like, by forming operations such as molding and extrusion.
• the expression substantially unstretched indicates that subsequent to the forming operation the articles have not been subjected to a stretching operation or, more specifically, to a stretching operation whereby any dimension of the articles is increased by more than 10%.
• stretched polypivalolactone can only be obtained by physically stretching a preformed article made of polypivalolactone.
• stretching excludes compressive deformation.
• a method for the manufacture of improved molded or extruded articles of polypivalolactone in which a molded or extruded article of substantially unstretched polypivalolactone containing a nucleating agent having a particle size of not more than 5 microns (i.e., when worked into and as present in the pivalolactone) is annealed without deformation other than shrink at a temperature of between and 230 C., preferably between and 200 C.
• Particularly preferred polylactones are the polymers obtained by polymerizing beta-lactones, particularly the alpha,alpha-dialkyl-beta-propio-lactones wherein the alkyl groups contain from 1 to 4 carbon atoms, including those compounds in which the two alkyl groups and the alphacarbon atom of the lactone ring are combined to form one cyclic structure, such as, for example, 2-oxa-4-spiro[3.6] decanone-l.
• Suitable examples include alpha,alpha-di methyl-beta-propiolactone, alpha-methyl-alpha-ethyl-betapropiolactone, alpha-methyl-alpha-isopropyl-beta-propiolactone, alpha-ethyl-alpha-tert-butyl-propiolactone, alpha, alpha-diisopropyl-propiolactone, etc.
• the most preferred alpha,alpha-dialkyl-beta propiolactone is alpha,alpha-dimethyl-beta-propiolactone (pivalolactone).
• the poly (beta-lactone) may be prepared by any conventional means, usually in the pesence of a suitable catalysts (see US. No. 3,021,309, US. No. 3,268,486, British No. 766,347, French No. 1,231,163, or Belgian No. 649,828).
• Suitable catalysts which may be used in polymerizing the beta-lactones include the primary, secondary, or tertiary amines such as trimethylamine, triethylamine, tri (beta-hydroxyethyl)amine, tripropylamine, triisopropylamine, methyldiethylamine, tri-n-butylamine, diethyl-nbutylamine, dimethylhexylamine, triphenylamine, diethylamine, di-n-propylamine, diisopropylamine, dibutylamine, monobutylamine, monophenylamine, triethylenediamine, hexamethylenetetraamine, and the like.
• primary, secondary, or tertiary amines such as trimethylamine, triethylamine, tri (beta-hydroxyethyl)amine, tripropylamine, triisopropylamine, methyldiethylamine, tri-n-butylamine, diethyl
• catalysts include quaternary ammonium compounds and especially the tetraalkylammonium halides or hydroxides where the alkyl groups contain from 1 to about 4 carbon atoms such as tetraethylammonium bromide, tetrapropylammonium bromide, ethyltriisopropylammonium chloride, tetraethylammonium hydroxide, etc.
• Suitable polymerization catalysts are the arsines, stibines and phosphines as well as the addition products thereof.
• Suitable catalysts of this type are those disclosed in copending US. application Ser. No. 363,992, now U.S. Pat. No. 3,268,486, filed Apr. 30, 1964, the description thereof which is incorporated herein by reference.
• tertiary phosphines and the quaternary phosphonium compounds such as trimethylphosphiue, triethylphosphine, tri(beta chloroethyl)phosphine, triphopylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, dimethylhexylphosphine, diethyl-n-pentylphosphine,
• the preferred polylactone is polypivalolactone.
• polypivalolactone is meant a thermoplastic resin which substantially consists of a linear polyester having recurring ester structural units of the formula
• the polyester may readily be prepared by the polymerization of pivalolactone (alpha,alpha-dimethyl-beta-propiolactone) as disclosed by Klootwijk in US. 3,268,486.
• the thermoplastic resin may consist of a polymer obtained from pivalolactone as the sole monomer or may consist of certain copolymers or polymer blends. Thus, copolymeric components may be present in the polyester in amounts of up to 25 mol. percent.
• the copolymeric units be grouped in blocks alternating with blocks of pivalolactone polymer.
• lactones are particularly suited, especially beta-propiolactones.
• the copolymers may be derived from copolymerization of pivalolactone with up to 25 mol. percent of alpha,alpha-diethyl-beta-propiolactone or alpha ethylalpha-methyl-beta-propiolactone.
• thermoplastic resins such as polyamides like nylon-6 or nylon-l2; polyesters like polyethyleneterephthalate; polyvinyl chloride; polyvinyl butyral; polyepoxides curing agent); polyolefins like polypropylene and chlorinated polyether resins like Penton.
• Suitable heat stabilizers include, among others, thiuram sulfides, dithiocarbamates and xanthogenates, such as copper (H), dimethyldithiocarbamate and tetramethylthiuram disulfide; copper salts of carboxylic acids having a tertiary or quaternary a-carbon atom, such as the copper (II) salt of Versatic 1519 (a commercially available carboxylic acid obtained by subjecting a mixture of C -C alpha-olefins to the Koch reaction); nitroso aromatic compounds, such as 2,4-dinitrosoresorcinol; and phosphites like tris- (nonylphenyD-phosphite and pentaerythritolpho
• phosphites are used in combination with one or more other heat stabilizers, such as the preferred combination of tetramethylthiuramdisulfide and tris(nonylphenyl)-phosphite.
• These stabilizers are generally used in amounts of 0.1-% by weight, preferably 0.2-2% by weight based on polypivalolactone. Adequate stabilization may thus be obtained by means of, e.g., 0.1% by weight of tetramethylthiuram disulfide and 0.4% by weight of trisnonylphenyl -pho sphite.
• light stabilizers such as benzophenones, e.g., 2-hydroxy-4-n-octoXy-benz0phenone, and benzotriazoles, e.g., 2-(2-hydroxyphenyl)-benzotriazole.
• benzophenones e.g., 2-hydroxy-4-n-octoXy-benz0phenone
• benzotriazoles e.g., 2-(2-hydroxyphenyl)-benzotriazole.
• These stabilizers may be used in amounts up to 2% by weight, preferably 0.1-1% by weight, based on polypivalolactone.
• Suitable fillers which may be employed as desired, include, among many others, aluminum powder, mica, bentonites, clays, synthetic resins and elastomers, ignited A1 0 short-fiber asbestos, wood flours, barytes, carbon black, silica, zinc dust, talc and the like. A large number of fillers are available commercially in particle sizes from about 0.1 micron upward.
• Other suitable fillers include the pigments which are chemically-stable inorganic or organic pigments such as titania, phthalocyanine blue or green, iron oxide and cadmium red.
• the quantity of fillers used is dependent upon many factors such as cost, particle size, particle shape, absorption characteristics and loading volume.
• the polypivalolactone used in the molding or extrusion of the articles possesses a relatively high molecular weight, i.e., the limiting viscosity number (LVN) will, in general, be above 0.75 dl/ g. (measured in benzyl alcohol at 135 C.), preferably above 2.0 dl./ g.
• the LVN is given by the formula:
• nucleating agents used in accordparticle size of not more than 5, preferably not more than 2% w. have, in general, a particle size of not more than 5, preferably not more than 1 micron. Very good results have been obtained with nucleating agents having a particle size of less than 30 millimicrons.
• nucleating agents which have needle-like crystals.
• nucleating agents may be used which have a melting point above 200 C., preferably above that of the polypivalolactone, which is in the range of 240- 250 C.
• the nucleating agent used will have a melting point above the annealing temperature employed. Suitable nucleating agents are, inter alia.
• fine metal powders such as aluminum, lead and electrolytic copper powder
• inorganic substances such as graphite, carbon black, glass fibers, asbestos, magnesia, silica, zinc oxide, titanium dioxide, barium sulfate, calcium or sodium carbonate, molybdenum disulfide, cobalt monosulfide, iron (II) sulfide, tungsten disulfide, calcium tungstate, alkali halides such as sodium chloride and lithium fluoride, talc, clay; coronene; pigments, such as flavanthrene, metal salts of sulfonated azo pigments and quinacridone.
• Preferred nucleating agents are:
• the compounds belonging to the above category (a) are boron nitride and the chlorides, bromides, and iodides of alkali metals, among which the sodium and potassium chlorides are particularly effective.
• boron nitride appears to have the strongest nucleating action and is therefore preferred.
• the compounds of category (b) comprise salts of organic acids containing a group which on one side is attached to an acidic hydroxyl group and on the other to an aromatic carbon atom.
• the Y atom in the above formula has been drawn as being tetravalent only, with a possible fifth or sixth valence bond having been omitted. This should, however, by no means he considered restrictive.
• Y representing a sulfur atom
• this atom may be both tetravalent and hexavalent.
• Y being a phosphorus atom
• pentavalent phosphorus is meant.
• the said group of organic acids comprises: carboxylic acids, sulfonic acids, sulfinic acids, phosphonic acids and phosphinic acids, in which the acidic hydroxyl group therefore forms part of the respective structures where the group R may be a hydrocarbon radical, for example an alkyl or aryl group.
• Particularly preferred compounds of category (b) are the salts of carboxylic acids, sulfonic acids, and phosphinic acids containing the group indicated above, with a hydrogen atom directly attached to phosphorus.
• Salts of acids containing a carboxyl group attached to an aromatic ring such as a naphthalene or a benzene ring have very attractive nucleating action. More specifically, the salts of benzenecarboxylic acids which carry as a substituent a tertiary alkyl group or a carboxyl group which may or may not be esterified have proved excellent nucleating agents. Examples of such active salts are salts of p-tert-butylbenzoic acid, phthalic acid, tetrachlorophthalic acid and salts of the monoalkyl esters of phthalic acid and tetrachlorophthalic acid.
• salts derived from naphthalenesulfonic acids such as the salts of naphthalene-l-sulfonic acid and naphthalene-Z-sulfonic acid.
• the mono-, bior trivalent metals in the aforementioned salts of organic acids are preferably the alkali metals and alkaline earth metals, among which special preference is given to potassium, sodium, and barium. It is further noted that the above discussion of the metal salts or organic acids exclusively refers to the neutral salts.
• the quantities in which the nucleating agents are present in the compositions according to the invention usually range from 0.0001 to percent by weight or more, calculated on weight of polypivalolactone. Quantities of from 0.01 to 2 percent by weight are preferred.
• the nucleating agent may be incorporated into the polypivalolactone by adding it to the pivalolactone to be polymerized. It is also possible, however, to add the nucleating agent to the polymeric material, i.e., to the polypivalo lactone powder, granules, nibs and the like, either before or during the forming operation.
• the nucleating agent is dry-mixed with polypivalolactone powder, e.g., in a Banbury mixer whereafter, if desired, the mixed powder may be extruded into nibs or pellets.
• Forming of the articles from the polypivalolactone containing the nucleating agent may be effected in any manner known for this purpose, provided the article is not being cold stretched, i.e., stretched at temperatures below about 230 C.
• articles may be made by compression or injecting molding or by extrusion.
• One method of compression molding consists, for example, in cold forming or forgeing polypivalolactone (powder, pellets, sheet, and the like) in a press at temperatures of 0235 C.
• the molded or extruded articles may be machined prior to annealing, e.g., by cutting, drilling, sawing, or grinding.
• Annealing of the article is effected without deformation other than shrink, either by heat-treating the article in an annealing oven or bath or by keeping the molded article for a fraction of a minute to several hours in the mold at a temperature of between 140 and 230 C. If desired, the articles may be subjected to alternate cooling and annealing cycles. It has been found that very good properties of the polypivalolactone may be obtained if the annealing treatment is carried out under such conditions that (unfilled) pivalolactone homopolymer reaches a density of at least 1.175 g./ml., preferably of at least 1.19 g./ml.
• the annealing temperature will depend on the annealing temperature how long the operation will have to be continued before the desired density is reached. In general, the annealing will take from a fraction of a minute to 12 hours or more, preferably from 0.530 minutes. The higher the temperature, the shorter the annealing time can be.
• the optimum combination of the annealing time and temperature is determined experimentally for a particular type of article, which will depend, inter alia, on the articles thickness and geometry.
• Minimum annealing temperatures have been found to be 15 seconds at 230 C., 1 minute at 180 C., 30 minutes at 160 C. and 3 hours at 140 C.
• annealing medium different heating units are used.
• liquid baths such baths usually consist of tanks or troughs filled with water, oils or waxes.
• gas-flow ovens have proved to be suitable.
• a non-oxidizing medium such as steam, nitrogen or carbon dioxide may be used as well as air.
• the gas is heated to the required temperature, then flows to another compartment in which the article is annealed.
• a proper method for slow and gradual cooling is suitably provided, preferably at a cooling rate of less than 15 C./ minute.
• a liquid annealing medium such as a highboiling hydrocarbon oil, fat or wax; synthetic oils such as fluorocarbons, silicone oils, glycol ethers and esters, and the like.
• a liquid annealing medium such as a highboiling hydrocarbon oil, fat or wax; synthetic oils such as fluorocarbons, silicone oils, glycol ethers and esters, and the like.
• such oils have a boiling point of at least 250 C. as well as adequate stability.
• EXAMPLE 13 The procedures of Examples 1-12 were substantially repeated wherein 0.1 phr. of the following nucleating agents were used in lieu of the sodium salt of alphanaphthalene sulfonic acid: sodium chloride, potassium chloride, boron nitride and silica. Related results were obtained.
• a method for the manufacture of shaped polylactone articles having improved physical properties wherein the polylactone is shaped the improvement which comprises annealing without deformation at a temperature between 140 and 230 C.
• the said shaped articles com prising a substantially unstretched poly(beta-lactone) and from 0.0001 to 5% by weight of a nucleating agent having a particle size of not more than 5 microns, wherein the term substantially unstretched means that said shaped articles have not been subjected to a stretching operation whereby any dimension is increased by more than 10%.
• annealing temperature is between 160 and 200 C.
• nucleating agent has the general formula MX, wherein X represents a halogen having an atomic number of a least 17 or nitrogen and M represents an alkali metal or boron.
• nucleating agent is sodium or potassium chloride.
• nucleating agent is boron nitride
• nucleating agent is a salt of a mono-, bior trivalent metal and an organic acid containing an acidic hydroxyl group attached to an aromatic carbon atom by means of a group with the structure

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)

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• 1967
  • 1967-02-24 GB GB8861/67A patent/GB1119755A/en not_active Expired
• 1968
  • 1968-02-09 US US704269A patent/US3577502A/en not_active Expired - Lifetime
  • 1968-02-22 DE DE19681694950 patent/DE1694950A1/de active Pending
  • 1968-02-22 FR FR1565512D patent/FR1565512A/fr not_active Expired
  • 1968-02-22 SE SE02284/68A patent/SE337464B/xx unknown
  • 1968-02-22 NL NL6802524A patent/NL6802524A/xx unknown
  • 1968-02-22 CH CH265768A patent/CH504502A/de not_active IP Right Cessation
  • 1968-02-22 ES ES350793A patent/ES350793A1/es not_active Expired
  • 1968-02-22 BE BE711126D patent/BE711126A/xx unknown
  • 1968-02-22 AT AT170768A patent/AT277585B/de active

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